Ring-opening Ziegler olefin polymerization catalysts and polymers therefrom

ABSTRACT

The regiospecific (1,2-Me 2  C 5  H 3 ) 2  ZrMe +  MeB(C 6  F 5 ) 3  - mediated ring-opening polymerization of methylenecyclobutane and its copolymerization with ethylene to polyolefins of microstructure --{CH 2  CH 2  CH 2  C(CH 2 )]-- n  and {--[CH 2  CHR]-- x  [CH 2  CH 2  CH 2  C(CH 2 )]-- y  } n , respectively is disclosed.

This is a continuation-in-part of application Ser. No. 962,390, filed Oct. 16, 1992, now U.S. Pat. No. 5,300,598 issued Apr. 5, 1994.

BACKGROUND OF THE INVENTION

This application relates to catalysts and more particularly to homogeneous catalysts for use in polymerization via the ring opening of strained ring systems, and the polymers formed with such catalysts.

In the presence of Ziegler-Natta catalysts, methylenecyclobutane A can be polymerized into a polymer consisting of a mixture of micro-structure units B and C, through a ring-opening mechanism and a simple vinyl type insertion mechanism, respectively. ##STR1## Micro-structure B is particularly interesting in that it not only represents the thermodynamically unstable form of the synthetic rubberopoly(isoprene), but when incorporated into copolymers with simple olefins, it can impart useful functionalities. Although it has been shown that several Ziegler-Natta catalysts, including AlEt₂ Cl--Cr(acac)₃ --TiCl₄ ARA, can selectively produce a polymer with structure B dominating, the activity of these catalysts appears extremely sluggish. More importantly, the mechanism of the ring-opening process which was earlier proposed to involve the oxidative addition of the ring C--C bond seems unlikely with the early transition metals where the required oxidation states may not necessarily be available.

SUMMARY OF THE INVENTION

Therefore, an object of the subject invention is a novel catalyst for polymerizations having a high activity.

A further object of the subject invention is a polymer formed from a catalytic olefin polymerization process which operates via a ring-opening mechanism.

A still further object of the subject invention is a polymer formed through the use of a catalyst by which electrophilic metallocene cations catalyze the facile regioselective ring-opening homopolymerization of exo-methylene substituted cyclic organic compounds and the copolymerization of such compounds with α-olefins such as ethylene, propylene and styrene via a β-alkyl shift mechanism.

Catalysts having RB(C₆ F₅)₃ -, B(C₆ F₅)₄ - or methylalumoxane derivatives as the charge-compensating anion, especially Cp₂ ZrMe⁺ MeB(C₆ F₅)₃ ⁻ (Cp=η-1,2-Me₂ C₅ H₃), can catalyze the ring-opening polymerization of methylenecyclobutane to form the iso-rubber micro-structure B with not only very high selectivity, but also great efficiency. Such Catalysts also catalyze the co-polymerization of simple olefins with exo-methylene cyclic organic monomers, such as methylenecyclobutane. Polyolefins of the structure [CH₂ CH₂ CH₂ C(CH₂)]_(n) and ([CH₂ CHR]_(x) [CH₂ CH₂ CH₂ C(CH₂)]_(y))_(n) can thus be prepared where R=an alkyl or aryl group. The probable mechanism of the methylenecyclobutane polymerization is shown in the Reaction Sequence I. ##STR2## The key step is a heretofore unrecognized ring opening polymerization via a β-alkyl shift. Such a polymerization process should be applicable to the polymerization of a variety of strained ring monomers having exocyclic unsaturation.

DETAILED DESCRIPTION OF THE INVENTION

Facile β-alkyl transpositions are a distinctive feature of electrophilic d^(o) f^(n) hydrocarbyl chemistry (e.g., equation (II)) and ##STR3## represent an important chain transfer channel in certain olefin polymerization processes. In principle, such transpositions might also provide an unusual pathway to functionalized polyolefins by coupling olefin insertion and strained monomer ring-opening sequences (equation (III)). ##STR4## In the presence of conventional heterogeneous Ziegler-Natta catalysts, methylenecyclobutane A undergoes a sluggish reaction to afford polymers having ring-opening or mixed ring-opening/insertion-derived microstructures (B,C). The ring-opened structures were ascribed to oxidative addition at the C3-C4/C4-C5 junctures of A. As stated above, the subject invention involves electrophilic zirconocene cations, which catalyze the facile, regioselective ring-opening homopolymerization of exo-methylene cyclic organic compounds and copolymerization with ethylene via a β-alkyl shift mechanism.

The exo-methylene cyclic organic compounds generally may be represented by the formula: ##STR5## where R^(I), R^(II), R^(III) and R^(IV) are organic fragments which may include O, N, S or P. Preferably, the monomer is methylenecyclobutane.

In general, reaction of the catalyst Cp_(n) MR⁺ _(3-n) B(C₆ H₅)₃ R'⁻, where Cp is a cyclopentadienyl containing ligand where n=1 or 2, M=Ti, Zr, or Hf, and R, R' is an alkyl (C=1-5), hydride, or aryl, with A proceeds rapidly in toluene solution to yield, after work-up, polymethylenecyclobutane (PMCB, Table I). Examples of viable catalysts are (C₅ H₅)₂ ZrMe⁺ MeB(C₆ F₅)₃ ⁻ and (1, 2 Me₂ C₅ H₃)₂ ZrMe⁺ MeB(C₆ F₅)₃ ⁻, or (C₅ H₅)₂ ZrR₂ and methylalumoxane, (R=alkyl, aryl, hydride, halide or alkoxide. Other nonpolar solvents, both aliphatic (C=1-12) and aromatic (C=6-20) as well as others may be used. ¹ H and ¹³ C NMR spectra reveal that the polymer microstructure is almost exclusively B (≧95%; minor traces of C may be present), indicating that the present polymerization is highly selective for the ring-opening pathway. The length of reaction time/extent of conversion appears to have no detectable effect on selectivity (Table I, entries 1, 2). However, lower reaction temperatures appear to slightly favor microstructure C (Table I, entry 3 by ¹ H NMR). NMR analysis also indicates allylic end groups in all of those PHCB samples, consistent with chain transfer via β-H elimination. The present PMCB samples are soluble in aromatic solvents, but insoluble in CHCI₃ or acetone.

Copolymerization of A with α-olefins such as ethylene can be readily effected by stirring A neat or in toluene solution with 1 under 1.0 atm of ethylene (Table I, entries 4-6). ¹ H and ¹³ C NMR spectroscopy indicates ##STR6## that the derived copolymers have ring-opened microstructure C exclusively and that the x and y proportions ##STR7## can be controlled via the reaction stoichiometry.

                                      TABLE 1                                      __________________________________________________________________________     Polymerization of Methylenecyclobutane and Copolymerization with Ethylene      Using                                                                          (1,2-Me.sub.2 C.sub.5 H.sub.3).sub.2 ZrMe.sup.+ MeB(C.sub.6 F.sub.5).sub.3      as a Catalyst                                                                          Methylene                                                                 Catalyst                                                                            cyclobutane                                                                           Ethylene           Yield of                                                                            Methylene                                  Amount                                                                              Amount Pressure                                                                            Solvent                                                                             Temp                                                                               Reaction                                                                            Polymer                                                                             cyclobutane:                                                                          M.sub.w (M.sub.n).sup.c         Entry                                                                              (umol)                                                                              (mmol) (1 atm)                                                                             (mL) (°C.)                                                                       Time (h)                                                                            (g)  ethylene.sup.b                                                                        × 1000                    __________________________________________________________________________     1   7.33 27.0   0.0  Toluene                                                                             20  16   1.7  --     83.3                                                 (10)          (100%).sup.a                                                                               (38.5)                          2   7.33 27.0   0.0  Toluene                                                                             20  5    1.1  --     n.a.                                                 (10)           (60%).sup.a                                3   7.33 23.8   0.0  Toluene                                                                             -30 20   0.16 --     n.a.                                                 (10)           (9%).sup.a                                 4   7.33 23.8   1.0  None 20  0.17 0.84 0.81   89.9                                                                           (35.5)                          5   7.33 8.3    1.0  Toluene                                                                             20  0.17 0.98 0.21   255.3                                                (15)                      (192.0)                         6   7.57 1.2    1.0  Toluene                                                                             20  0.12 0.60 ca. 0.002                                                                             n.a.                            __________________________________________________________________________      .sup.a Monomer conversion by .sup.1 H NMR.                                     .sup.b Ratio of methylenecyclobutane and ethylene incorporated into the        copolymer as determined by .sup.1 H NMR.                                       .sup.c By GPC versus polystyrene.                                        

Various functionalized polymers are possible through the use of the catalyst of the subject invention, which results in a ring-opening Ziegler polymerization. Examples of the possible polymers are set forth in Table 2. The recurring exomethylene group is a signature group in the resulting polymer and is a focal point for additional functionalization or crosslinking.

                  TABLE 2                                                          ______________________________________                                         MonomerPolymer                                                                 ______________________________________                                          ##STR8##                                                                       ##STR9##                                                                       ##STR10##                                                                      ##STR11##                                                                      ##STR12##                                                                      ##STR13##                                                                     ______________________________________                                    

(R, R¹ =alkyl group (C=1-5) or phenyl group.)

All operations were performed with rigorous exclusion of oxygen and moisture in flamed Schlenk-type glassware in a dual manifold Schlenk line or interfaced to a high vacuum (10⁻⁵ torr) system, or in a nitrogen or argon filled glovebox with a high capacity atmosphere recirculator. Argon, ethylene and propylene were purified by passage through a supported MnO oxygen removal column and a molecular sieve column. Aliphatic hydrocarbon solvents were pretreated with concentrated H₂ SO₄, KMnO₄ solution, MgSO₄ and Na, 4 Å molecular sieves. All reaction solvents were distilled from Na/K/benzophenone under nitrogen and were condensed and stored in vacuo in bulbs on the vacuum line containing a small amount of [Ti(η⁵ -C₅ H₅)₂ Cl]₂ ZnCl₂ as indicator. Methylenecyclobutane was additionally dried over Na/K.

EXAMPLES Preparation of Catalyst Synthesis of Cp"₂ ZrMe₃ +Me₃ B(C₆ F₅)₃ ⁻ (Cp"=1,2Me₂ C₅ H₃)

CP"₂ ZrMe₂ (0.116 g, 0.378 mmol) and B(C₆ F₅)₃ (0.194 g, 0.379 mmol) are loaded into a 25 mL flask. Benzene (10 mL) was then vacuum transferred into this flask at -78° C. As the mixture was slowly warmed to ambient temperature. A clear solution was first seen but it quickly became cloudy as solids began to precipitate. After stirring for 2.5 h, the mixture was filtered. The light yellow solid was washed once with a small amount of benzene and dried under vacuum. Yield, 65%.

Synthesis of Cp₂ ZrCH₃ ⁺ CH₃ B(C₆ F₅)₃ ⁻ (Cp=η⁵ -C₅ H₅)

Cp₂ ZrMe₂ (0.100 g, 0.398 mmol) and B(C₆ F₅)₃ (0.205 g, 0.400 mol) are loaded into a 25 mL flask in the glovebox. Benzene (15 mL) was then vacuum-transferred into this flask at -78° C. The mixture was slowly warmed to room temperature and stirred for 1.5 h. At this time large quantities of solid precipitated. Pentane (10 mL) was vacuum-transferred into the flask and the mixture was filtered after stirring. The light yellow solid was washed once with 5 mL of pentane and dried under vacuum. Yield, 72%.

Alternately, Cp₂ ZrMe₂ (0.264 g, 1.052 mmol) and B(C₆ F₅)₃ (0.539 g, 1.055 mmol) may be stirred in 20 mL of pentane in a 50 mL flask for 12 h at room temperature. The mixture is filtered and the solid washed once with pentane and dried under vacuum. Yield, 81%.

EXAMPLE 1 Homo-polymerization of Methylenecyclobutane

(1,2-Me₂ C₅ H₃)₂ ZrMe⁺ MeB(C₆ F₅)₃ ⁻ (6 mg) was loaded into a 25 mL flask in a glovebox. Toluene (10 mL) and methylenecyclobutane (2.4 mL) were vacuum-transferred into the above flask at -78° C. The flask was backfilled with Ar and the solution stirred at room temperature for 16 h. The reaction was then quenched with methanol. After removing the volatiles under vacuum, the elastomeric polymeric product was washed several times with toluene and dried under vacuum. Yield 1.73 g. The polymer is characterized by ¹ H and ¹³ C NMR spectroscopy. The ¹ H NMR also gives an number-averaged molecular weight (M_(n)) of ca.2,000.

EXAMPLE 2 Co-polymerization of Methylenecyclobutane with Ethylene

(1,2-Me₂ C₅ H₃)₂ ZrMe⁺ MeB(C₆ F₅)₃ ⁻ (6 mg) was loaded into a 25 mL flask in a glovebox. Toluene (10 mL) and methylenecyclobutane (0.70 mL) were vacuum-transferred into the above flask at -78° C. The solution was stirred at room temperature under 1 atm of ethylene for 10 min. The reaction was then quenched with methanol. The white solid product was collected by washing with acetone and drying under vacuum. Yield 0.98 g. NMR (toluene-d₈, 90° C.): ¹ H : δ(PPM) 4.83, 2.06, 1.65, 1.50, 1.35. ¹³ C: δ(ppm) 150.2, 149.9, 109.5, 109.3, 36.9, 36.4, 30.16, 28.48, 26.78.

EXAMPLE 3 Co-polymerization of Methylenecyclobutane with Ethylene

(C₅ H₅)₂ ZrMe⁺ MeB(C₆ F₅)₃ ⁻ (25.8 mg) was loaded into a 25 mL flask in the glovebox. Toluene (25 mL) and methylenecyclobutane (0.10 mL) were vacuum-transferred into the above flask at -78° C. The solution was stirred at room temperature under 1 atm of ethylene for 2.0 min. The reaction was then quenched with methanol. The white solid product was collected by washing with acetone and drying under vacuum. Yield 0.68 g.

EXAMPLE 4 Homo-polymerization of Exomethylene Cyclobutane Cyclopentane

(1,2-Me₂ C₅ H₃)₂ ZrMe⁺ MeB(C₆ F₅)₃ ⁻ (6 mg) is loaded into a 25 mL flask in a glovebox. Toluene (10 mL) and exomethylene cyclobutane cyclopentane (1.0 mL) are vacuum-transferred into the above flask at -78° C. The flask is backfilled with Ar and the solution stirred at room temperature for 10 h. The reaction is then quenched with methanol. After removing the volatiles under vacuum, the elastomeric polymeric product is washed several times with acetone and dried under vacuum. Yield should be about 0.49 g. The polymer is characterized by ¹ H and ¹³ C NMR spectroscopy.

EXAMPLE 5 Homo-polymerization of Exomethylene Cyclobutane Benzene

(1,2-Me₂ C₅ H₃)₂ ZrMe⁺ MeB(C₆ F₅)₃ ⁻ (6 mg) is loaded into a 25 mL flask in a glovebox. Toluene (10 mL) and exomethylene cyclobutane benzene (1.0 mL) are vacuum-transferred into the above flask at -78° C. The flask is backfilled with Ar and the solution stirred at room temperature for 10 h. The reaction is then quenched with methanol. After removing the volatiles under vacuum, the polymeric product is washed several times with acetone and dried under vacuum. Yield should be about 0.39 g. The polymer is characterized by ¹ H and ¹³ C NMR spectroscopy.

EXAMPLE 6 Homo-polymerization of Methyl Exomethycyclobutane

(1,2-Me₂ C₅ H₃)₂ ZrMe⁺ MeB(C₆ F₅)₃ ^(-l) (6 mg) is loaded into a 25 mL flask in a glovebox. Toluene (10 mL) and methyl exomethylcyclobutane (2.0 mL) are vacuum-transferred into the above flask at -78° C. The flask is backfilled with Ar and the solution stirred at room temperature for 20 h. The reaction is then quenched with methanol. After removing the volatiles under vacuum, the elastomeric polymeric product is washed several times with acetone and dried under vacuum. Yield should be about 1.2 g. The polymer is characterized by ¹ H and ¹³ C NMR spectroscopy.

EXAMPLE 7 Co-polymerization of Ethylene and Methylenecyclopropane

(1,2-Me₂ C₅ H₃)₂ ZrMe MeB(C₆ F₅)₃ (14 mg) was loaded into a 50 mL flask in the glove box. Then 20 mL of toluene and 0.25 mL of liquid methylenecyclopropane were vacuum box. Then 20 mL of toluene and 0.25 mL of liquid methylenecyclopropane were vacuum transferred into it. The solution was stirred under 1 atm of ethylene at room temperature for 5 minutes. It was quenched with methanol. The product was collected by filtration, washed with acetone and dried under vacuum. Yield 0.40 g. It was characterized by H¹ NMR in toluene-d⁸ at 110° C.

EXAMPLE 8 Co-polymerization of Ethylene and Methylenecyclopropane

(C₅ Me₅)₂ ZrMe MeB(C₆ F₅)₃ (15 mg) was loaded into a 50 mL flask in the glove-box. Then 15 mL of toluene was vacuum transferred into it. The solution was stirred under a mixture of ethylene and methylenecyclopropane (ratio 1:1 by volume) at room temperature for 20 minutes. It was quenched with methanol. The product was collected by filtration, washed with acetone and dried under vacuum. Yield 0.29 g. It was characterized by H¹ NMR in toluene-D⁸ AT 100° C.

EXAMPLE 9 Co-polymerization of Ethylene and Methylenecyclopropane

(C₅ Me₅)₂ ZrMe MeB(C₆ F₅)₃ (15 mg) was loaded into a 50 mL flask in the glove-box. Then 15 mL of toluene was vacuum transferred into it. The solution was stirred under a mixture of ethylene and methylenecyclopropane (ratio 3:1 by volume) at 60° C. for 25 minutes. It was quenched with methanol. The product was collected by filtration, washed with acetone and dried under vacuum. Yield 0.30 g. It was characterized by H¹ NMR in toluene-d⁸ at 110° C.

With regard to the polymerization mechanism, it seems unlikely, based upon known chemistry, that methylenecyclobutane can support two-electron (or one-electron) oxidative addition-reductive elimination propagation sequences. Furthermore, ¹ H and ¹³ C NMR analysis of copolymerizations with ¹³ CH₂ ═¹³ CH₂ indicates the presence of one ¹³ --CH₂ -- unit adjacent to every exo-methylene group, compatible only with a C₂ -C₃ /C₂ -C₅ ring opening. Combined with prior evidence for β-Me shifts in propylene polymerizations at cationic zirconocene centers and β-alkyl shift-based methylenecyclobutane →1,4-pentadiene rearrangements at isoelectronic scandocene centers, the pathways of Reaction Sequence I set forth above seem most compatible with the present results. Additionally, kinetic measurements ([1]=1.57-15.7 mm [A]=1.05-2.09M) reveal that the homopolymerization of A obeys rate law (IV), where ##EQU1## K=4.1 (1)×10⁻² M⁻¹ S⁻¹ at -5.5° C. Thus the turnover-limiting step under these conditions appears to be olefin insertion rather than cyclobutane ring opening. As a result, it would appear that β-alkyl shift processes represent an efficient propagation pathway for the synthesis of new exo-methylene-functionalized polyolefins.

While the invention has been described with reference to a preferred embodiment, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from the essential scope thereof. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed as the best mode contemplated for carrying out this invention, but that the invention will include all embodiments and equivalents falling within the scope of the appended claims.

Various features of the invention are set forth in the following claims. 

We claim:
 1. A polymer having a repeating unit selected from the group consisting of ##STR14## where R, R¹ =alkyl group (C=1-5), phenyl group, or H, and said polymer has a molecular weight of at least about
 83000. 2. A copolymer having the repeating unit --AB-- where A is an α-olefin and B is an exo-methylene substituted cyclic organic compound and said polymer has a molecular weight of at least about 89,000.
 3. The copolymer of claim 2 wherein A is selected from the group consisting of ethylene, propylene, and styrene.
 4. The copolymer of claim 2 where B is selected from the group consisting of ##STR15##
 5. A copolymer as in claim 1 having the repeating units --CH₂ --CH₂ -- and ##STR16##
 6. The polymer of claim 1 wherein the molecular weight is about 83,000.
 7. The copolymer of claim 1 wherein the molecular weight is from about 89,000 to about 255,000. 